CN110407235A - The preparation method of electric car stage monohydrate lithium hydroxide - Google Patents
The preparation method of electric car stage monohydrate lithium hydroxide Download PDFInfo
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
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Abstract
The present invention relates to the preparation methods of electric car stage monohydrate lithium hydroxide, belong to technical field of lithium batteries.The technical problem to be solved by the present invention is to provide the preparation methods of electric car stage monohydrate lithium hydroxide.This method handled by slurries, neutralizes purification, deliming twice, except magnetic and except organic matter, concentration, convert, be refining to obtain EV stage monohydrate lithium hydroxide.The method of the present invention, EV stage monohydrate lithium hydroxide can successfully be prepared, realize the industrialized production of EV stage monohydrate lithium hydroxide, entire process flow closed circulation, reduce supplies consumption, reduce production cost, the loss of lithium is small, product yield is high, total recovery is not less than 90%, there is no three waste discharge, it is environmentally friendly, obtained product quality is excellent, compared with LITHIUM BATTERY product, its chemical index is more excellent, magnetisable material is lower, it is less easy to reunite, and there is excellent homogeneity of product, for the capacity for improving lithium dynamical battery, battery life and its security performance lay a solid foundation.
Description
Technical field
The present invention relates to the methods of the preparation method of electric car stage monohydrate lithium hydroxide, belong to technical field of lithium batteries.
Background technique
Under the overall background such as energy restriction, environmental pollution, the whole world will be using development new energy as improvement environment, save the cost
Important measure.Wherein, new-energy automobile (electric car) with use low in cost, maintenance is easy, manufacture difficulty is lower,
The incomparable advantages such as the strong, low-carbon environment-friendly of smooth ride power, become the developing direction of future automobile industry.According to Chinese vapour
Vehicle Industry Association announce data show, 1-11 month in 2017, pure electric automobile production and marketing 52.6 ten thousand and 50.2 ten thousand, on year-on-year basis
Increase by 56.5% and 60.9%, 2018 2 month new-energy automobile volume of production and marketing be respectively 39230 and 34420, increase by a year-on-year basis
119.19% and 95.2%.With the continuous renewal of technology, electric car cruising ability is more and more stronger, and safety coefficient is increasingly
High, service life is increasingly longer, these will all be attributed to the fact that electric car to the high standards of power battery.
A link of the power battery as new-energy automobile most critical, the breakthrough of technology will will lead to Global Auto production
Industry transition and upgrade realizes spanning development.As the lithium salts product of power battery raw materials for production, quality will be to power battery
Performance has a huge impact.Inventor is devoted for years to propose LITHIUM BATTERY list water in the research of lithium battery specialized lithium product salt
Lithium hydroxide product and production method.For example, patent CN10214978A discloses the preparation side of battery-stage monohydrate lithium hydroxide
Method is added sodium hydroxide and obtains Na using lithium sulfate scavenging solution as raw material2SO4·10H2O solid and LiOH liquid, then pass through separation
Liquid crystalization obtains LiOHH2Crude product of O, then by LiOHH2After crude product dissolution of O, refining agent refining reaction is added,
Filtrate is filtered to take, crystallisation by cooling is concentrated by evaporation, obtains solid, is dried, as LITHIUM BATTERY LiOHH2O product.
This method is the production method of battery grade lithium product salt, with the raising that electric car requires, existing LITHIUM BATTERY
Lithium salts product is difficult meet the needs of electric automobile power battery again, and therefore, it is necessary to a kind of new electric car grades (i.e. EV grades)
Monohydrate lithium hydroxide, to meet the needs of electric car.The product of EV stage monohydrate lithium hydroxide and battery-stage monohydrate lithium hydroxide
Quality is shown in Table 1.
Table 1
As it can be seen from table 1 the requirement of EV stage monohydrate lithium hydroxide product purity, impurity content and magnetisable material content
It is higher than LITHIUM BATTERY, and existing industrial process, it can only obtain the product of LITHIUM BATTERY.Therefore, it is badly in need of EV grades of single water hydrogen
The production method of lithia product.
Summary of the invention
For disadvantages described above, the technical problem to be solved by the present invention is to provide a kind of systems of electric car stage monohydrate lithium hydroxide
The method of Preparation Method, in this way, EV stage monohydrate lithium hydroxide product can be prepared.
The method of the preparation method of electric car stage monohydrate lithium hydroxide of the present invention, includes the following steps:
A, slurries are handled: after the filtering of lithium sulfate slurries, calcium carbonate being added in filtrate, is separated by solid-liquid separation, obtains two hydrations
Calcium sulphate solid and subacidity liquid, wherein the lithium sulfate slurries are that resulting leaching slurry is leached after lithium ore is acidizing fired,
The pH value of lithium sulfate slurries is 1~2, and specific gravity is 1.2~1.4, and concentration is with Li2O content is calculated as 30~32g/L；
B, neutralize purification twice: the subacidity liquid pH for adjusting step A is 6.5~7.5, reacts 30~40min, and filtering obtains
To neutral solution；Then in neutral solution, sodium carbonate is added, and adjusting pH is 11~12, reacts 30~40min, filtering obtains one
Secondary scavenging solution；
C, deliming, except magnetic and remove organic matter: by the primary purification liquid of step B by the deliming of cation resin exchange film,
Magnetic is removed by low temperature, organic matter is removed by adsorbent, filtering obtains double purification liquid and purification slag；
D, it is concentrated: by the double purification liquid of step C by concentration, obtaining concentrate, the concentration of concentrate is with Li2O is calculated as
43~45g/L；
E, the acquisition of lithium hydroxide: being added sodium hydroxide in a concentrate of D step, then freeze, and is separated by solid-liquid separation,
Obtain lithium hydroxide liquid and saltcake solid；
F, the purification twice of lithium hydroxide: after the lithium hydroxide liquid evaporation condensing crystallizing of E step, crystallisation by cooling, mistake
Filter, obtains fine work of lithium hydroxide；By fine work deionized water dissolving of lithium hydroxide, evaporating, concentrating and crystallizing, cooling knot
Crystalline substance, filtering, obtains the secondary fine work of lithium hydroxide；
G, the purification three times of lithium hydroxide: the secondary fine work of lithium hydroxide is spent into ionized water dissolution, is added and removes sodium refining agent
Except sodium, sulfate radical is removed by nanofiltration membrane, is then crystallized, the super magnetic of high temperature, is separated by solid-liquid separation, obtains lithium hydroxide fine work three times；
H, four purifications of lithium hydroxide: by lithium hydroxide, fine work is dry three times, then carries out electricity and removes magnetic, obtains hydroxide
Four fine work of lithium；
I, electricity removes magnetic: after four fine work of lithium hydroxide are levigate, then carrying out electricity except magnetic, obtains electric car grade list water hydroxide
Lithium；
Wherein, it is 90~100 DEG C that low temperature, which removes the temperature of magnetic, and magnetic field strength is 10000~12000Gs；The temperature of the super magnetic of high temperature
Degree is 120~150 DEG C, and magnetic field strength is 16000~18000Gs；Electricity is 18000~20000Gs except the magnetic field strength of magnetic.
Preferably, in deionized water by the saltcake solid dissolution of E step, evaporating, concentrating and crystallizing, filtering obtains anhydrous sodium sulphate
With LiOH mother liquor, LiOH mother liquor is returned in step B to adjust pH value.
Preferably, in step A, the additional amount of calcium carbonate is 12~16kg/m3Filtrate.
Preferably, in step B, sodium carbonate is added in the form of a solution, and the concentration of sodium carbonate liquor is 300 ± 10g/L, carbonic acid
The additional amount of sodium solution is 1.5~2 liters/side neutral solution.
Preferably, the adsorbent of step C is aluminum silicon powder；It is preferred that the additional amount of aluminum silicon powder be primary purification liquid quality 1~
3%.
Preferably, in D step, the concentration is concentrated using film；It is preferred that concentration is dense using low temperature distillation LMD film progress film
Contracting.
In G step, except sodium refining agent is preferably Li1.3Ti0.8Ce0.4Zr0.5Al0.3(PO4)3Or
Li1.3Zr0.8Ce0.4Si0.5Al0.3(PO4)3, except the additional amount of sodium refining agent is Na in solution+20~25 times of quality, when reaction
Between be 30~60 minutes.
Preferably, in H step, fine work is dried using vacuum belt drier in 75~85 DEG C lithium hydroxide three times.
It is further preferred that dispersing agent is added in lithium hydroxide three times fine work, then be dried in H step；It is preferred that institute
Stating dispersing agent is polyethylene glycol, and the additional amount of dispersing agent is 0.2~0.5wt%.
Preferably, in I step, four fine work of lithium hydroxide are levigate using purification air progress, and then electricity removes magnetic, clean
Packaging, obtains electric car stage monohydrate lithium hydroxide；CO in the purification air2Volume content is 0.005~0.01%.
Compared with prior art, the invention has the following beneficial effects:
1) EV stage monohydrate lithium hydroxide no currently on the market can be successfully prepared in the method for the present invention, realize EV grades
The industrialized production of monohydrate lithium hydroxide.
2) Recycling Mother Solution of the invention uses, and entire process flow closed circulation reduces supplies consumption, reduces production
The loss of cost, lithium is small, and product yield is high, and total recovery is environmentally friendly without three waste discharge not less than 90%.
3) film concentration technique is applied to lithium industry by the method for the present invention, reduces energy consumption, reduces production steam bring
Environmental pollution；Resin and UF membrane calcium, magnesium technology are applied to lithium industry, reduce organic substance residues to the shadow of product quality
It rings.
4) product quality that the method for the present invention obtains is excellent, is EV grades of products, compared with LITHIUM BATTERY product, chemical index
More excellent, magnetisable material is lower, less easy to reunite, and has excellent homogeneity of product, for capacity, the electricity for improving lithium dynamical battery
Pond service life and its security performance lay a solid foundation.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of electric car stage monohydrate lithium hydroxide of the present invention.
Specific embodiment
The method of the preparation method of electric car stage monohydrate lithium hydroxide of the present invention, includes the following steps:
A, slurries are handled: after the filtering of lithium sulfate slurries, calcium carbonate being added in filtrate, is separated by solid-liquid separation, obtains two hydrations
Calcium sulphate solid and subacidity liquid, wherein the lithium sulfate slurries are that resulting leaching slurry is leached after lithium ore is acidizing fired,
The pH value of lithium sulfate slurries is 1~2, and specific gravity is 1.2~1.4, and concentration is with Li2O content is calculated as 30~32g/L；
B, neutralize purification twice: the subacidity liquid pH for adjusting step A is 6.5~7.5, reacts 30~40min, and filtering obtains
To neutral solution；Then in neutral solution, sodium carbonate is added, and adjusting pH is 11~12, reacts 30~40min, filtering obtains one
Secondary scavenging solution；
C, deliming, except magnetic and remove organic matter: by the primary purification liquid of step B by the deliming of cation resin exchange film,
Magnetic is removed by low temperature, organic matter is removed by adsorbent, is most filtered afterwards through micro-pipe, obtains double purification liquid and purification slag；It is described
Low temperature is 90~100 DEG C except the temperature of magnetic, and magnetic field strength is 10000~12000Gs；
D, it is concentrated: by the double purification liquid of step C by concentration, obtaining concentrate, the concentration of concentrate is with Li2O is calculated as
43~45g/L；
E, the acquisition of lithium hydroxide: being added sodium hydroxide in a concentrate of D step, then freeze, and is separated by solid-liquid separation,
Obtain lithium hydroxide liquid and saltcake solid；
F, the purification twice of lithium hydroxide: after the lithium hydroxide liquid evaporation condensing crystallizing of E step, crystallisation by cooling, mistake
Filter, obtains fine work of lithium hydroxide；By fine work deionized water dissolving of lithium hydroxide, evaporating, concentrating and crystallizing, cooling knot
Crystalline substance, filtering, obtains the secondary fine work of lithium hydroxide；
G, the purification three times of lithium hydroxide: the secondary fine work of lithium hydroxide is spent into ionized water dissolution, is added and removes sodium refining agent
Except sodium, sulfate radical is removed by nanofiltration membrane, is then crystallized, the super magnetic of high temperature, is separated by solid-liquid separation, obtains lithium hydroxide fine work three times；
H, four purifications of lithium hydroxide: by lithium hydroxide, fine work is dry three times, then carries out electricity and removes magnetic, obtains hydroxide
Four fine work of lithium；
I, electricity removes magnetic: after four fine work of lithium hydroxide are levigate, then carrying out electricity except magnetic, obtains electric car grade list water hydroxide
Lithium；
Wherein, it is 90~100 DEG C that low temperature, which removes the temperature of magnetic, and magnetic field strength is 10000~12000Gs；The temperature of the super magnetic of high temperature
Degree is 120~150 DEG C, and magnetic field strength is 16000~18000Gs；Electricity is 18000~20000Gs except the magnetic field strength of magnetic.
The method of the present invention, using specific technique removal of impurities and certain working procedure remove magnetic, by acidity except magnetic (i.e. adjusting sulphur
Remove magnetic in sour lithium slurries pH1~2)；Purification is neutralized twice removes Si, Fe, Al, Ca, Mg；Film concentration；Adsorb de- organic impurities；Specific work
The low temperature of sequence is superpower except magnetic and electricity remove magnetic except magnetic, high temperature；Refining agent removes sodium；The programs such as film sulphur removal complete electric car (EV) grade
The preparation of industrialization of monohydrate lithium hydroxide.Its main reaction principle and theory are as follows:
Li2SO4+2NaOH+12H2O (freezing)=2LiOHH2O+Na2SO4·10H2O↓
Serial reaction is typical precipitation reaction, and product has water, precipitating or gas, reacts and carries out to positive direction.Below
It describes in detail respectively to each step.
Step A is the processing of slurries.The present invention uses lithium sulfate slurries to handle for raw material, and lithium sulfate slurry is preferably adopted
It is leached with efficient: quantitative water is added in the lithium sulfate solid clinker containing 2~3% residual acid, lithium sulfate slurry specific gravity is made to exist
1.2~1.4, concentration is with Li2O content is calculated as 30~32g/L.Keep its pH value 1~2, it is ensured that acidity removes magnetic.
The lithium sulfate slurries are filtered, minimal amount of iron and lithium, the powder of as low iron lithium are contained in filter residue.After filtration
Filtrate in calcium carbonate is added, can react to obtain CaSO4·2H2O precipitating.Preferably, in step A, calcium carbonate adds
Entering amount is 12~16kg/m3Filtrate.
Step B is the step of neutralizing purification twice.Impurity is precipitated in adjusted stepwise pH value, main that following reaction occurs:
Fe3++3OH-=Fe (OH)3↓
Al3++3OH-=Al (OH)3↓
Cu2++2OH-=Cu (OH)2↓
Zn2++2OH-=Zn (OH)2↓
Fe2++2OH-=Fe (OH)2↓
Ni2++2OH-=Ni (OH)2↓
Co2++2OH-=Co (OH)2↓
Mn2++2OH-=Mn (OH)2↓
Mg2++2OH-=Mg (OH)2↓
Ca2++CO3 2-=CaCO3↓
Preferably, in step B, sodium carbonate is added in the form of a solution, and the concentration of sodium carbonate liquor is 300 ± 10g/L, carbonic acid
The additional amount of sodium solution is 1.5~2 liters/side neutral solution.
Step B, which adjusts pH value, can use NaOH or LiOH, it is preferred that adjust pH value, LiOH mother liquor using LiOH mother liquor
For by the dissolution of the saltcake solid of E step, in deionized water, evaporating, concentrating and crystallizing, filtering, obtained solid is anhydrous sodium sulphate, liquid
As LiOH mother liquor, LiOH mother liquor are preferably returned in step B to adjust pH value.The LiOH Recycling Mother Solution to lithium sulfate is neutralized
Cleaning procedure reduces the consumption of material compared with prior art, to the stabilization for keeping electric car stage monohydrate lithium hydroxide quality
Property improves a lot.
In general, the amount that LiOH mother liquor is added is 3~8 liters/side, and LiOH mother liquor is added in secondary neutralization when once neutralizing
Amount is 35~45 liters/side.
Step C is principally obtaining the process of double purification liquid.By lithium sulfate primary purification liquid obtained in the previous step, pass through sun
Ion exchange resin carries out depth deliming, guarantees [Ca in outlet liquid2+] between 1~3ppm, by 90~100 DEG C of low temperature,
The liquid that magnetic field strength is 10000~12000Gs removes magnetic machine, by resistant to high temperature organic miscellaneous in adsorbent removing system
Matter, and it is filtered separation through micro-pipe, obtain double purification liquid.Preferably, the adsorbent is aluminum silicon powder (Al2O3·SiO2·
nH2O), it is furthermore preferred that the additional amount of adsorbent aluminum silicon powder is the 1~3% of primary purification liquid quality.
D step is concentration process.It is preferred that lithium sulfate double purification liquid is concentrated by film, with process product after raising
Yield rate, by lithium sulfate solution from Li230~32g/L of O concentration is promoted to 43~45g/L, obtains concentrate.Preferably, film
Concentration uses low temperature distillation LMD film.Film concentration technique is used in lithium industry, traditional evaporation and concentration is substituted, about 2/3 can be reduced
Energy consumption, reduce production the environmental pollution of steam bring.
The preferred concrete operations of E step are as follows: sodium hydroxide, preferably hydroxide is added in a concentrate of D step
The additional amount of sodium is 65.2~66.8kg/m3, conversion fluid is obtained, conversion fluid is cooled to 20~25 DEG C and is delivered to refrigeration system,
Conversion fluid generates freezing magma after being refrigerated to -3~-6 DEG C, by freezing magma centrifuge separation, mother liquor passes through settler overflow, overflows
Clear liquid filtering generation freezing clear liquid is flowed out to obtain, clear liquid, that is, lithium hydroxide liquid is freezed and enters lithium hydroxide flush distillation process, and
Saltcake crystal heating for dissolving is isolated to obtain, re-evaporation condensing crystallizing extracts anhydrous sodium sulphate, and resulting LiOH mother liquor returns to Li2SO4Purification
Process.
F-step is that subtractive process, evaporating, concentrating and crystallizing therein are preferably MV evaporating, concentrating and crystallizing to lithium hydroxide twice.
G step is the subtractive process three times of lithium hydroxide.The step removes sodium using refining agent, film depth separates sulfate radical,
Compared with prior art, sodium and sulfate radical in product is made to be reduced to 30ppm or less.
Preferably, except sodium refining agent is Li1.3Ti0.8Ce0.4Zr0.5Al0.3(PO4)3Or Li1.3Zr0.8Ce0.4Si0.5Al0.3
(PO4)3, except the additional amount of sodium refining agent is Na in solution+20~25 times of quality, reaction time are 30~60 minutes, control Na
And SO4 2-Between 1~2g/L, which is directly reduced to 30ppm or less for sodium in product and sulfate radical content.
Preferably, the crystallization of G step is crystallized using MVR stable state, control loop pump circulation amount and centrifuge separation feed liquid temperature,
Feed liquid temperature control is centrifugated at 40~45 DEG C.The generation of agglomeration can be prevented in this way.
Preferably, in H step, fine work is dried using vacuum belt drier in 75~85 DEG C lithium hydroxide three times.
Reunite in order to prevent, it is preferred that in H step, dispersing agent is added in lithium hydroxide three times fine work, then done
It is dry.It is furthermore preferred that the dispersing agent is polyethylene glycol, such as polyethylene glycol-400 PYCF or polyethylene glycol -600PYCS, dispersion
The additional amount of agent is 0.2~0.5wt%.
In order to preferably prevent reuniting, in I step, it is gentle that four fine work use purification air of lithium hydroxide convey
Stream crushing is levigate, and then electricity removes magnetic, purifies CO in air2Volume content is 0.005~0.01%, can be reduced using molecular sieve
Water and carbon dioxide content in air.
Clean packaging of the present invention is that automatic packaging operation is carried out in 100,000 grades of clean rooms, ensure that mistake entirely
Journey is in dry and without the environment for influencing quality, and no extraneous magnetisable material and mechanical admixture enter in product, ensure that final production
Quality reaches EV grades of requirement.
In the method for the present invention, according to material properties, temperature of charge and product characteristics, it is respectively adopted acid except magnetic, low temperature remove
The super magnetic of magnetic, high temperature and electricity remove magnetic, reach EV stage monohydrate lithium hydroxide product magnetisable material in 50ppb or less.In the present invention, it removes
The acidity of step A is in addition to magnetic, remaining is all made of existing liquid or solid except magnetic machine except magnetic, and low temperature removes the temperature of magnetic
Degree is 90~100 DEG C, and magnetic field strength is 10000~12000Gs；The temperature of the super magnetic of high temperature is 120~150 DEG C, and magnetic field strength is
16000~18000Gs；Electricity is 18000~20000Gs except the magnetic field strength of magnetic.
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1
As shown in Figure 1, producing to obtain EV stage monohydrate lithium hydroxide using following steps:
A, slurries are handled: after the filtering of lithium sulfate slurries, 12kg/m being added in filtrate3Calcium carbonate, be separated by solid-liquid separation, obtain
To calcium sulphate dihydrate solid and subacidity liquid, wherein the lithium sulfate slurries are that leaching is resulting after lithium ore is acidizing fired
Leaching slurry, the pH value of lithium sulfate slurries are 1, and specific gravity 1.2, concentration is with Li2O content is calculated as 30g/L.
B, neutralize purification twice: the subacidity liquid pH for adjusting step A is 6.5, reacts 30min, and filtering obtains neutral solution；
Then in neutral solution, addition concentration is 1.5 liters of 300 ± 10g/L sodium carbonate liquor/side's neutral solution, and adjusting pH is 11, reaction
30min, filtering, obtains primary purification liquid.
C, deliming, except magnetic and remove organic matter: by the primary purification liquid of step B by the deliming of cation resin exchange film,
Magnetic is removed by low temperature, passes through the high-efficiency activated aluminum silicon powder Al of adsorbent2O3·SiO2·nH2O removes organic matter, the dosage of adsorbent
It is the 1% of primary purification liquid quality, is most filtered afterwards through micro-pipe, obtain double purification liquid and purification slag；The low temperature removes the temperature of magnetic
Degree is 90 DEG C, magnetic field strength 10000Gs.
D, film is concentrated: (low temperature distillation LMD film) is concentrated by film in the double purification liquid of step C, obtains concentration with Li2O
It is calculated as the concentrate of 43g/L.
E, sodium hydroxide 65.2kg/m the acquisition of lithium hydroxide: is added in the concentrate of D step3, conversion fluid is obtained, it will
Conversion fluid is cooled to 20 DEG C and is delivered to refrigeration system, and conversion fluid generates freezing magma, will freeze magma after being refrigerated to -3 DEG C
Centrifuge separation, mother liquor pass through settler overflow, and overflow goes out to obtain clear liquid filtering generation freezing clear liquid, freezes clear liquid, that is, lithium hydroxide liquid
Body into subsequent K step, and isolates to obtain saltcake crystal heating for dissolving, and re-evaporation condensing crystallizing extracts anhydrous sodium sulphate, remaining mother liquor
For LiOH mother liquor, return in step B to adjust pH value.
F, the purification twice of lithium hydroxide: after the lithium hydroxide liquid MV evaporating, concentrating and crystallizing of J step, crystallisation by cooling,
It is separated by filtration, obtains fine work of lithium hydroxide.
By fine work deionized water dissolving of lithium hydroxide, MV evaporating, concentrating and crystallizing, crystallisation by cooling is separated by filtration, obtains
To the secondary fine work of lithium hydroxide.
G, the purification three times of lithium hydroxide: the secondary fine work of lithium hydroxide is spent into ionized water dissolution, is added and removes sodium refining agent
Except sodium Li1.3Ti0.8Ce0.4Zr0.5Al0.3(PO4)3, except the additional amount of sodium refining agent is Na in solution+20 times of quality, when reaction
Between be 30 minutes, by nanofiltration membrane remove sulfate radical, then crystallize, the super magnetic of high temperature, separation of solid and liquid, it is smart three times to obtain lithium hydroxide
Product.The temperature of the super magnetic of high temperature is 120 DEG C, magnetic field strength 16000Gs.
H, four purifications of lithium hydroxide: by lithium hydroxide, fine work uses vacuum belt drier to do in 75 DEG C three times
It is dry, it then carries out electricity and removes magnetic, obtain four fine work of lithium hydroxide；The electricity is 18000Gs except the magnetic field strength of magnetic.
I, clean packaging: by four fine work of lithium hydroxide using purification air (CO2Volume content is 0.005~0.01%)
Conveying and air-flow crushing are carried out, then electricity removes magnetic, and clean packaging obtains electric car stage monohydrate lithium hydroxide.
Resulting electric car stage monohydrate lithium hydroxide is detected, EV grades of requirement is met, specific testing result is shown in Table 2.
Embodiment 2
As shown in Figure 1, producing to obtain EV stage monohydrate lithium hydroxide using following steps:
A, slurries are handled: after the filtering of lithium sulfate slurries, 16kg/m being added in filtrate3Calcium carbonate, be separated by solid-liquid separation, obtain
To calcium sulphate dihydrate solid and subacidity liquid, wherein the lithium sulfate slurries are that leaching is resulting after lithium ore is acidizing fired
Leaching slurry, the pH value of lithium sulfate slurries are 2, and specific gravity 1.4, concentration is with Li2O content is calculated as 32g/L.
B, neutralize purification twice: the subacidity liquid pH for adjusting step A is 7.5, reacts 40min, and filtering obtains neutral solution；
Then in neutral solution, addition concentration is 2 liters of 300 ± 10g/L sodium carbonate liquor/side's neutral solution, and adjusting pH is 12, reaction
40min, filtering, obtains primary purification liquid.
C, deliming, except magnetic and remove organic matter: by the primary purification liquid of step B by the deliming of cation resin exchange film,
Magnetic is removed by low temperature, passes through the high-efficiency activated aluminum silicon powder Al of adsorbent2O3·SiO2·nH2O removes organic matter, the dosage of adsorbent
It is the 3% of primary purification liquid quality, is most filtered afterwards through micro-pipe, obtain double purification liquid and purification slag；The low temperature removes the temperature of magnetic
Degree is 100 DEG C, magnetic field strength 12000Gs.
D, film is concentrated: (low temperature distillation LMD film) is concentrated by film in the double purification liquid of step C, obtains concentration with Li2O
It is calculated as the concentrate of 45g/L.
E, sodium hydroxide 66.8kg/m the acquisition of lithium hydroxide: is added in the concentrate of D step3, conversion fluid is obtained, it will
Conversion fluid is cooled to 25 DEG C and is delivered to refrigeration system, and conversion fluid generates freezing magma, will freeze magma after being refrigerated to -6 DEG C
Centrifuge separation, mother liquor pass through settler overflow, and overflow goes out to obtain clear liquid filtering generation freezing clear liquid, freezes clear liquid, that is, lithium hydroxide liquid
Body into subsequent K step, and isolates to obtain saltcake crystal heating for dissolving, and re-evaporation condensing crystallizing extracts anhydrous sodium sulphate, remaining mother liquor
For LiOH mother liquor, return in step B to adjust pH value.
F, the purification twice of lithium hydroxide: after the lithium hydroxide liquid MV evaporating, concentrating and crystallizing of J step, crystallisation by cooling,
It is separated by filtration, obtains fine work of lithium hydroxide.
By fine work deionized water dissolving of lithium hydroxide, MV evaporating, concentrating and crystallizing, crystallisation by cooling is separated by filtration, obtains
To the secondary fine work of lithium hydroxide.
G, the purification three times of lithium hydroxide: the secondary fine work of lithium hydroxide is spent into ionized water dissolution, is added and removes sodium refining agent
Except sodium Li1.3Zr0.8Ce0.4Si0.5Al0.3(PO4)3, except the additional amount of sodium refining agent is Na in solution+25 times of quality, when reaction
Between be 60 minutes, by nanofiltration membrane remove sulfate radical, then crystallize, the super magnetic of high temperature, separation of solid and liquid, it is smart three times to obtain lithium hydroxide
Product.The temperature of the super magnetic of high temperature is 150 DEG C, magnetic field strength 18000Gs.
H, four purifications of lithium hydroxide: by lithium hydroxide, fine work uses vacuum belt drier to do in 85 DEG C three times
It is dry, it then carries out electricity and removes magnetic, obtain four fine work of lithium hydroxide.The electricity is 20000Gs except the magnetic field strength of magnetic.
I, clean packaging: by four fine work of lithium hydroxide using purification air (CO2Volume content is 0.005~0.01%)
Conveying and air-flow crushing are carried out, then electricity removes magnetic, and clean packaging obtains electric car stage monohydrate lithium hydroxide.
Resulting electric car stage monohydrate lithium hydroxide is detected, EV grades of requirement is met, specific testing result is shown in Table 2.
Table 2
Comparative example 1
Using LITHIUM BATTERY lithium hydroxide product as raw material, by battery-stage monohydrate lithium hydroxide product, using the country
The grid iron remover of 8000Gs removes magnetic, can play certain effect, but should be very fast except the decaying of chinaware, and except chinaware is in high tender feeling
Under condition, magnetic field strength fluctuation is very big, and product magnetisable material content can only control within the scope of 300~1000ppb, be unable to reach
The requirement of EV stage monohydrate lithium hydroxide.
Claims (10)
1. the preparation method of electric car stage monohydrate lithium hydroxide, which comprises the steps of:
A, slurries are handled: after the filtering of lithium sulfate slurries, calcium carbonate being added in filtrate, is separated by solid-liquid separation, obtains two hydrated sulfuric acids
Calcium solid and subacidity liquid, wherein the lithium sulfate slurries are that resulting leaching slurry, sulfuric acid are leached after lithium ore is acidizing fired
The pH value of lithium slurries is 1~2, and specific gravity is 1.2~1.4, and concentration is with Li2O content is calculated as 30~32g/L；
B, neutralize purification twice: the subacidity liquid pH for adjusting step A is 6.5~7.5, reacts 30~40min, and filtering obtains
Property liquid；Then in neutral solution, sodium carbonate is added, and adjusting pH is 11~12, reacts 30~40min, filtering obtains primary net
Change liquid；
C, deliming, except magnetic and remove organic matter: by the primary purification liquid of step B by the deliming of cation resin exchange film, pass through
Low temperature removes magnetic, removes organic matter by adsorbent, filtering obtains double purification liquid and purification slag；
D, it is concentrated: by the double purification liquid of step C by concentration, obtaining concentrate, the concentration of concentrate is with Li2O is calculated as 43~
45g/L；
E, the acquisition of lithium hydroxide: being added sodium hydroxide in a concentrate of D step, then freeze, and is separated by solid-liquid separation, obtains
Lithium hydroxide liquid and saltcake solid；
F, the purification twice of lithium hydroxide: after the lithium hydroxide liquid evaporation condensing crystallizing of E step, crystallisation by cooling, filtering is obtained
To fine work of lithium hydroxide；By fine work deionized water dissolving of lithium hydroxide, evaporating, concentrating and crystallizing, crystallisation by cooling, mistake
Filter, obtains the secondary fine work of lithium hydroxide；
G, the purification three times of lithium hydroxide: spending ionized water dissolution for the secondary fine work of lithium hydroxide, is added except sodium refining agent removes sodium,
Sulfate radical is removed by nanofiltration membrane, is then crystallized, the super magnetic of high temperature, is separated by solid-liquid separation, obtains lithium hydroxide fine work three times；
H, four purifications of lithium hydroxide: by lithium hydroxide, fine work is dry three times, then carries out electricity and removes magnetic, obtains lithium hydroxide four
Secondary fine work；
I, electricity removes magnetic: after four fine work of lithium hydroxide are levigate, then carrying out electricity except magnetic, obtains electric car stage monohydrate lithium hydroxide；
Wherein, it is 90~100 DEG C that low temperature, which removes the temperature of magnetic, and magnetic field strength is 10000~12000Gs；The temperature of the super magnetic of high temperature is
120~150 DEG C, magnetic field strength is 16000~18000Gs；Electricity is 18000~20000Gs except the magnetic field strength of magnetic.
2. the method for the preparation method of electric car stage monohydrate lithium hydroxide according to claim 1, it is characterised in that: will
In deionized water, evaporating, concentrating and crystallizing, filtering obtains anhydrous sodium sulphate and LiOH mother liquor, and LiOH is female for the saltcake solid dissolution of E step
Liquid returns in step B to adjust pH value.
3. the method for the preparation method of electric car stage monohydrate lithium hydroxide according to claim 1, it is characterised in that: A
In step, the additional amount of calcium carbonate is 12~16kg/m3Filtrate.
4. the method for the preparation method of electric car stage monohydrate lithium hydroxide according to claim 1, it is characterised in that: B
In step, sodium carbonate is added in the form of a solution, and the concentration of sodium carbonate liquor is 300 ± 10g/L, and the additional amount of sodium carbonate liquor is
1.5~2 liters/side neutral solution.
5. the method for the preparation method of electric car stage monohydrate lithium hydroxide according to claim 1, it is characterised in that: C
The adsorbent of step is aluminum silicon powder；It is preferred that the additional amount of aluminum silicon powder is the 1~3% of primary purification liquid quality.
6. the method for the preparation method of electric car stage monohydrate lithium hydroxide according to claim 1, it is characterised in that: D
In step, the concentration is concentrated using film；It is preferred that concentration carries out film concentration using low temperature distillation LMD film.
7. the method for the preparation method of electric car stage monohydrate lithium hydroxide according to claim 1, it is characterised in that: G
In step, except sodium refining agent is Li1.3Ti0.8Ce0.4Zr0.5Al0.3(PO4)3Or Li1.3Zr0.8Ce0.4Si0.5Al0.3(PO4)3, remove sodium
The additional amount of refining agent is Na in solution+20~25 times of quality, reaction time are 30~60 minutes.
8. the method for the preparation method of electric car stage monohydrate lithium hydroxide according to claim 1, it is characterised in that: H
In step, fine work is dried using vacuum belt drier in 75~85 DEG C lithium hydroxide three times.
9. the method for the preparation method of electric car stage monohydrate lithium hydroxide according to claim 1, it is characterised in that: H
In step, dispersing agent is added in lithium hydroxide three times fine work, then be dried；It is preferred that the dispersing agent is polyethylene glycol, point
The additional amount of powder is 0.2~0.5wt%.
10. the method for the preparation method of electric car stage monohydrate lithium hydroxide according to claim 1, it is characterised in that: I
In step, four fine work of lithium hydroxide are levigate using purification air progress, and then electricity removes magnetic, and clean packaging obtains electronic vapour
Vehicle stage monohydrate lithium hydroxide；CO in the purification air2Volume content is 0.005~0.01%.
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